Actinic and electron beam radiation curable electrode binders and electrodes incorporating same

ABSTRACT

A process for manufacturing an electrode utilizing electron beam (EB) or actinic radiation to cure electrode binding polymers is provided. A process is also disclosed for mixing specific actinic or EB radiation curable chemical precursors with electrode solid particles, application of the mixture to an electrode current collector, followed by the application of actinic or EB radiation to the current collector for curing the polymer, thereby binding the electrode material to the current collector. Lithium ion batteries, electric double layer capacitors, and components produced therefrom are also provided.

CROSS REFERENCE TO RELATED APPLICATION

The present application claims filing benefit of U.S. Provisional PatentApplication Ser. No. 61/249,382 having a filing date of Oct. 7, 2009,which is incorporated herein by reference in its entirety.

FIELD OF THE DISCLOSURE

The present invention is in the technical field of electrodes as may beutilized in alkali-ion secondary (rechargeable) batteries, andparticularly in the technical field of lithium ion secondary batteries,and in electric double layer capacitors and manufacture thereof.

BACKGROUND

Electrochemical devices including batteries and electric double layercapacitors (EDLCs) have found great usefulness in power supplies,including power supplies of portable devices and auxiliary powersupplies for automobiles. For example, lithium ion batteries are one ofthe most popular battery types for use in portable electronics such asphones, music players, portable computers, and so forth. Lithium ionbatteries have very high energy-to-weight ratios, no memory effect, anda slow loss of charge when not in use. Lithium ion batteries are alsogrowing in popularity for military, electric vehicle, and aerospaceapplications due to their high energy density.

The basic working unit of a lithium ion battery is an electrochemicalcell. The electrochemical cell includes two electrodes, an anode andcathode, separated and connected by an electrolyte. The anode typicallyis a thin metal sheet of electrically conducting material, such ascopper, which is referred to as the anode current collector and iscoated with solid anode material particles. The solid particles are heldto the anode current collector and to each other by a binding material,which is typically a polymer which retains adhesion and hardness anddoes not swell or disintegrate during use. Typical anode particlesinclude carbon (generally graphite) and silicon-based materials. Theparticle sizes of the anode material coated on the current collectorrange from several nanometers to several microns in nominal diameter.

The lithium ion battery electrolyte may be liquid, solid or a gel. Forliquid electrolytes, a separator is employed to separate the anode fromthe cathode. A typical separator is a thin porous polymer sheet. Voidspaces in the polymer are filled with electrolyte. A typical liquidelectrolyte is a mixture of organic carbonates such as alkyl carbonatecontaining complexes of lithium ions, generally non-coordinated anionsalts such as lithium hexafluorophosphate (LiPF₆), lithiumhexafluoroarsenate monohydrate (LiAsF₆), lithium perchlorate (LiClO₄),lithium tetrafluoroborate (LiBF₄), and lithium triflate (LiCF₃SO₃).Typical solid electrolytes are polymers. A wide variety of materials maybe used as a gel electrolyte. The electrolytes are designed to withstandthe voltage between the anode and the cathode, and offer a high mobilityof lithium ions without a risk of flammability.

The cathode typically employed in a lithium ion battery includes a thinmetal sheet of electrically conducting material such as aluminum, whichis referred to as the cathode current collector, and is coated withsolid cathode particles. Cathode solid particles are held to the cathodecurrent collector and to each other by a solid polymer binding material,which is typically a polymer produced to retain adhesion and hardnessand not swell or disintegrate during use. Typical cathode materialsinclude particles of metal oxides such as lithium, cobalt, manganese,nickel, or vanadium oxides, and other lithium compounds such as lithiumiron phosphate. The cathode materials often include a small amount ofcarbon as well, to improve conductivity, though the carbon willgenerally not be as graphitic as that of the anode. Particle sizes ofthe cathode material coated on the current collector range from severalnanometers to several microns in nominal diameter.

An EDLC, also known as a supercapacitor or an ultracapacitor, is anelectrochemical capacitor that has an unusually high energy density whencompared to traditional capacitors. An EDLC includes two separateelectrodes of the same construction separated by an interveningsubstance that provides effective separation of charge despite avanishingly thin (on the order of nanometers) physical separation of thelayers. The electrode of an EDLC employs a current collector, typicallya current collector similar to that of a lithium ion battery cathode,such as aluminum. To improve energy storage density a nanoporousmaterial, typically a particulate carbon such as graphite or activatedcharcoal, is applied to the surface of the current collector with abinder, which is typically a polymer produced to retain adhesion andhardness and not swell or disintegrate during use. The particle size ofthe carbon generally ranges from several nanometers to several micronsin nominal diameter. The pores of the electrode carbon are then filledwith the intervening substance, i.e., an electrolyte that is a liquid ora gel. A typical liquid electrolyte is an organic alkyl carbonate thatcan include selected lithium salts.

A typical process for forming an electrode such as is found in a lithiumion battery or an EDLC includes:

-   -   1) The polymeric binding material is formed into a solution with        a solvent such that the solution has a suitably low viscosity        for application to the current collector after mixing with the        solid particles.    -   2) The low viscosity binding solution is mixed with the        electrode solid particles at approximately 20-80 wt. % of the        solvent, and particularly approximately 50 wt. % of the solvent        to form a paste.    -   3) The paste is coated in a thin layer (typically 10 to 200        microns) onto the current collector using conventional coating        techniques.    -   4) The coated current collector is passed through a thermal        drying oven where solvent is driven off and the binder polymer        is set.    -   5) The electrode is passed through a pair of rotating rollers        separated by a narrow gap (e.g. 5 to 200 microns) to compress        the current collector coating to a specified thickness.    -   6) Typically, both sides of the electrode current collector are        coated with anode/cathode particles and processed by the        aforementioned steps.

There are multiple shortcomings of the aforementioned prior art involvedin the manufacturing of electrodes that have a direct effect on the costof manufacturing. These shortcomings include, without limitation:

-   -   a) Solvent used to dissolve the polymer binding material must be        vaporized requiring substantial thermal energy input.    -   b) Substantial energy inefficiencies associated with thermal        drying.    -   c) The vaporized solvent must be recovered and either disposed        of or recycled.    -   d) The oven required for drying the polymer binding material        occupies significant manufacturing space at a significant        capital cost.    -   e) The time required to manufacture the electrodes is increased        by the time required for the polymer binding material to be        dried in the drying oven.

What are needed in the art are improved materials and methods forforming electrodes. For instance, improved binding materials for use inlithium ion cathodes and anodes and EDLC electrodes would be of greatuse.

SUMMARY

According to one embodiment, disclosed is an electrode including acurrent collector and a crosslinked polymeric layer adhered to a surfaceof the current collector. The polymeric layer can include a crosslinkedmatrix formed of a rubber polymer. For example, the rubber polymer caninclude monomeric units of isoprene, butadiene, cyclopentadiene,ethylidene norbornene, vinyl norbornene, or combinations thereof.Beneficially, the crosslinked matrix can be formed via actinic radiationor electron beam (EB) curing. As such, the crosslinked matrix can alsoinclude a reacted actinic radiation or EB curable crosslinking agentcovalently bonded to the crosslinked rubber polymer.

The crosslinked polymeric layer also includes particulate material. Theparticulate material can be carbon such as graphene, activated carbon,graphite, low sulfur graphite, carbon nanotubes, or combinationsthereof. The crosslinked polymer layer can include particulate materialsuch as a metal oxide salt, a lithium compound, or the like.

Electrodes can optionally be held adjacent to additional layers such asa second electrode, a separator, an electrolyte layer, and so forth. Byway of example, an electrode can be adjacent another layer in a battery,e.g., a lithium ion battery, or in an electric double layer capacitor(EDLC).

Methods of forming the electrodes are also disclosed. For instance, amethod can include mixing a binder coating composition with an electrodeparticulate material to form a mixture. The binder coating compositioncan include a functionalized rubber polymer. In addition, the bindercoating composition can include a crosslinking agent capable of formingcovalent bonds upon subjection to actinic or EB radiation. The bindercoating composition can have a melt viscosity of less than about 20Pascal seconds, so as to be capable of forming a coating layer.

The method can also include applying the mixture to a surface of acurrent collector to form a layer, and subjecting the layer of themixture to actinic or electron beam radiation, thereby crosslinking thefunctionalized rubber polymer.

The binder coating composition can include additional materials such asa reactive diluent, a wetting agent, a photoinitiator, and so forth. Inone embodiment, the crosslinking agent can also function as a diluent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a plan view of one embodiment of an electrode manufacturingprocess as disclosed herein.

FIG. 2 is a plan view of another embodiment of an electrodemanufacturing process as disclosed herein.

FIG. 3 is a cross-sectional view of a lithium ion electrochemical cellaccording to one embodiment of the disclosure.

FIG. 4 is a cross-sectional view of an EDLC according to one embodimentof the disclosure.

FIG. 5 is an initial charge and discharge curve of an electrochemicalcell formed as disclosed herein.

FIG. 6 is an initial charge and discharge curve of anotherelectrochemical cell formed as disclosed herein.

FIG. 7 is an initial charge and discharge curve of anotherelectrochemical cell formed as disclosed herein.

DETAILED DESCRIPTION

Reference now will be made in detail to various embodiments of thedisclosed subject matter, one or more examples of which are set forthbelow. Each example is provided by way of explanation, not limitation,of the subject matter. In fact, it will be apparent to those skilled inthe art that various modifications and variations may be made in thepresent disclosure without departing from the scope or spirit of thedisclosure. For instance, features illustrated or described as part ofone embodiment, may be used on another embodiment to yield a stillfurther embodiment. Thus, it is intended that the present disclosurecover such modifications and variations.

In general, the present disclosure is directed to a process formanufacturing electrodes without the need for the costly oven-drying orsolvent handling described above and to products such as lithium ionbatteries, EDLCs and other products as may incorporate the electrodes.More specifically, disclosed electrodes incorporate a polymeric bindingmaterial that can be cured with actinic radiation or electron beam (EB)radiation. As utilized herein, the term actinic radiation is intended torefer to electromagnetic radiation that is capable of producingphotochemical effects. For instance, disclosed polymeric bindingmaterials can be cured by actinic radiation in the ultraviolet (UV) orvisible spectrum, both of which can encompass actinic radiation. Aprocess is also disclosed for mixing actinic radiation or EB curablechemical precursors with solid particles and applying the mixture to anelectrode current collector, followed by the subjection of the coatedcurrent collector to suitable radiation to so as to covalently crosslinkand cure the polymer, thereby binding the particles to one another aswell as to the crosslinked polymeric matrix and also binding theelectrode material to the current collector.

To date, conventional UV and EB curable binder resins have not beenutilized successfully in electrode manufacturing. Generally, this isunderstood to be due to the extreme conditions present in operatingconditions for the electrodes, e.g., the heat and corrosive nature of alithium ion battery. The majority of conventional binder resins havepoor adhesion to metals and/or poor chemical resistance to, forinstance, electrolyte material.

Disclosed herein are functionalized polymers that are EB and/or actinicradiation curable and may be utilized as binders in electrodemanufacturing. Disclosed polymeric materials demonstrate good adhesionto current collectors (e.g. copper or aluminum) while providing thenecessary resistance to harsh operating conditions and electrolyticmaterial present in both batteries and EDLCs.

According to one embodiment, functionalized polymers can be based onrubber polymers. Exemplary rubbers suitable for use includefunctionalized polyisoprene and/or polybutadiene rubbers. U.S. Pat. No.4,218,349, incorporated herein by reference, describespolyisoprene-based rubber compositions and the manufacture thereof thatmay be suitable for use in the present invention. U.S. Pat. No.5,300,569, incorporated herein by reference, describespolybutadiene-based rubber compositions and the manufacture thereof thatmay be suitable for use in the present invention. However, disclosedbinders are not limited to rubbers incorporating only isoprene and/orbutadiene polymers. Functionalized rubber oligomers and polymers as maybe utilized in forming the binders can include at least one of isoprene,butadiene, cyclopentadiene, ethylidene norbornene, and vinyl norbornenemonomer units, or combinations thereof.

The rubber polymers or oligomers can be functionalized to includereactive groups that improve metal adhesion and/or improve curability byEB or actinic radiation crosslinking. For instance, carboxylated,acrylated, vinyl, vinyl ether, or epoxy functionalized polyisopreneand/or polybutadiene rubbers that are curable with electron beam oractinic ultraviolet radiation can be used. Exemplary functionalizedpolymers are commercially available, for instance, as Isolene® resinsfrom Elementis, Hightstown, N.J.; Trilene® resins from Chemtura,Middlebury, Conn.; liquid isoprene rubbers (LIR) from Kuraray Co.Pasadena, Tex., and liquid butadiene rubbers (LBD) such as Kraysol®,Ricon®, Riacryl®, and Polybd® resins from Sartomer Co., Exton, Pa. orBAC resins from San Esters, New York, N.Y.

In one embodiment, a binder can have an isoprene backbone with one ormore reactive functional groups pendent thereto. These binders have beenfound to yield exemplary results as a polymeric binder in formingelectrodes, for instance cathodes and anodes useful in lithium ionbatteries. One embodiment of suitable binders incorporate a carboxylatedmethacrylated isoprene backbone having the general formula:

wherein m is between about 10 and about 1000, or between about 100 andabout 1000, or between about 200 and about 500; and n is between 1 andabout 20, or between 1 and about 10, or between about 2 and about 10, orbetween about 2 and about 5.

Another embodiment of suitable binders incorporate a carboxylatedmethacrylated butadiene backbone having the general formula:

wherein m is between about 10 and about 1000, or between about 100 andabout 1000, or between about 200 and about 500; and n is between 1 andabout 20, or between 1 and about 10, or between about 2 and about 10, orbetween about 2 and about 5.

Another embodiment of suitable binders incorporate a butadiene backbonehaving the general formula:

wherein n is between about 5 and about 2000, or between about 10 andabout 1500, or between about 100 and about 1000.

Of course, binders can include multiple different backbone segments. Forinstance isoprene-butadiene copolymers are encompassed herein. Binderscan generally have a molecular weight from about 7,000 to about 110,000,or from about 10,000 to about 100,000, or from about 10,000 to about50,000, or from about 15,000 to about 40,000.

The rubber binder polymers can be included in a binder coatingcomposition in an amount from about 20 wt. % to about 100 wt. %, fromabout 25 wt. % to about 75 wt. %, from about 30 wt. % to about 70 wt. %,or from about 40 wt. % to about 60 wt. % of the binder coatingcomposition.

Suitable functionalized isoprene-based and butadiene-based rubbers caninclude, without limitation, grades UC-102, UC-105, and UC-203,available from Kuraray Ca, Pasadena, Tex.; and oligomers sold under thedesignation CN301, CN303, and CN307 available from Sartomer Co., Exton,Pa.

Actinic radiation/EB curable polymer binders as disclosed herein canhave a melt viscosity (at 38° C.) of less than about 2000 Pa·s, forinstance from about 5 to about 500 Pa·s, or from about 20 to about 200Pa·s. In forming an electrode from disclosed binders, a reactive diluentmay be added in order to lower the viscosity for ease of coating.Depending upon the characteristics of the polymer, a reactive diluentmay be added to lower the viscosity of the binder coating composition toless than about 10 Pa·s, for instance less than about 5 Pa·s, less thanabout 1.5 Pa·s, or less than about 1 Pa·s. As utilized herein, the termbinder coating composition is intended to refer to a composition forapplication to a current collector prior to cure that does not includeany particulate material to be applied to the current collector inconjunction with the binder coating composition. For instance, the termbinder coating composition refers to the composition prior to anypremixing with lithium metal oxide particulates or graphite particulatesand prior to cure.

While it will be appreciated that polymers having a melt viscosityhigher than about 2000 Pa·s may be utilized, a large amount of diluentwould be needed to reduce the binder coating composition to a suitablecoating viscosity. If the amount of diluent is greatly in excess of theamount of polymer, processing difficulties may be encountered and thedesired properties of the crosslinked polymeric binder may be moredifficult to attain. In general a reactive diluent may be present inamounts up to about 90 wt. %, for instance from about 10 wt. % to about90 wt. %, from about 25 wt. % to about 75 wt. %, or from about 40 wt. %to about 60 wt. % of the binder coating composition. A diluent can beselected so as to not degrade the quality of adhesion to the currentcollector or the chemical resistance properties of the binder. Inaddition, a diluent can have properties such that it is compatible withand will not substantially separate from the polymeric binder, forinstance during mixing and application of the binder coatingcomposition.

A reactive diluent can react with the functionalized rubber polymer tocrosslink the matrix during the cure. Accordingly, reactive diluents mayalternatively be referred to as crosslinking agents throughout thisdisclosure. Examples of reactive diluents encompassed herein include,but are not limited to isobornyl acrylate, polyethylene glycoldiacrylate, hexanediol diacrylate, alkyoxylatedhexanedioldiacrylate, andany other compound such as an acrylate that can both react with thefunctionalized rubber reactants during the cure and lower the meltviscosity of the binder coating composition.

A binder coating composition can include one or more crosslinking agentsthat do not necessarily also function as a diluent. For example, apolymer having a suitably low melt viscosity can be crosslinked by useof a crosslinking agent that does not also function as a diluent.Moreover, a polymeric binder coating composition can includecombinations of crosslinking agents, for example, both a reactivediluent crosslinking agent and a crosslinking agent that does not alsoact as diluent; two or more different reactive diluent crosslinkingagents, two or more crosslinking agents that do not also function as adiluent, and so forth.

Exemplary reactive crosslinking agents of a binder coating compositioncan include those that can react when subjected to EB and/or actinicradiation. Specific radiation suitable for each crosslinker is generallyknown in the art. For instance, a crosslinker can react upon subjectionwith actinic radiation in the UV spectrum or in the visible spectrum.Examples of crosslinking agents can include, without limitation,monofunctional acrylates, difunctional acrylates, and multifunctionalacrylates and other vinyl compounds. Suitable acrylates may be linear,branched, cyclic, or aromatic. Linear acrylates can include alkylacrylates wherein the alkyl contains from 4 to 20 carbon atoms. Branchedacrylates can include branched alkyl acrylates wherein the alkylcontains from 4 to 20 carbon atoms such as 2-ethylhexyl acrylate orisostearyl acrylate. Cyclic acrylates can include dicyclopentanylacrylate and n-vinyl caprolactam. Aromatic acrylates can includephenoxyethylacrylate. Difunctional and multifunctional acrylates caninclude 1,6-hexandiodi(meth)acrylate, 1,9-hexandiodi(meth)acrylate, andtricyclodecanedimethanol diacrylate.

The polymeric binder can be crosslinked in conjunction with aphotoinitiator. For instance, a photoinitiator can be a component of adiluent composition. A photoinitiator may be present in a binder coatingcomposition at concentrations up to about 20 wt. %, for instance fromabout 1 wt. % to about 15 wt. %, from about 1 wt. % to about 10 wt. %,or from about 1 wt. % to about 7 wt. % of the binder coatingcomposition.

Exemplary photoinitiators can include benzophenone, hydroxyacetophenone,methylbenzophenone, 4-Phenylbenzophenone, 4,4′-Bis(diethylamino)benzophenone, Michler's Ketone,4-(2-hydroxyethoxy)phenyl-(2-hydroxy-2-methylpropyl)ketone, and otherbenzophenone derivatives, benzyldimethyl ketal,2-benzyl-2-N,N-dimethylamino-1-(4-morpholinophenyl)-1 butanone;2-mercaptobenzoxazole, camphorquinone,2-hydroxy-2-methyl-1-(4-t-butyl)phenylpropan-1-none,2-methyl-1-[4-(methylthiophenyl)-2-morholinopropanone, maleimides,2,4,5-trimethylbenzoly-diphenyl phosphine oxides,bis(2,6-dimethyloxybenzoyl) 2,4,4-trimethylpentyl)phosphine oxide,bis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide, polymericphotoinitiators derived from the above, and combinations thereof. In oneembodiment, a propanone photoinitiator may be utilized such as a blendof about 70 wt. %oligo(2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone and about30 wt. % 2-hydroxy-2-methyl-1-phenylpropan-1-one, commercially availablefrom Lamberti USA, Inc., Conshohocken, Pa. under the trade name Esacure®KIP 150 or KIP 100F. Other photoinitiators sold by Lamberti USA, Inc.under the KIP or Esacure® designation may also be utilized, such asEsacure SM 303. Other polymeric photoinitiators include PL-816A fromPalermo Lundahl Industries. In another embodiment, an oxidephotoinitiator may be utilized. One suitable oxide photoinitiator isbis(2,4,6-trimethylbenzoyl)-phenylphosphineoxide commercially availablefrom Ciba Specialty Chemicals, Tarrytown, N.Y. under the trade nameIrgacure® 819. Other photoinitiators sold by Ciba Specialty Chemicalsunder the Irgacure® trade name are also suitable for use.

The binder coating composition may optionally include other processingagents suitable for the desired properties of the coating. Processingagents may be utilized in the coating composition up to about 10 wt. %,in some embodiments up to about 5 wt. %, and in some embodiments up toabout 2 wt. % of the binder coating composition. Processing agents thatmay be suitable for use in a binder coating composition can include,without limitation, coupling agents and adhesion promoters. A suitablecoupling agent is γ-glycidoxypropyltrimethoxysilane such as Silquest®A-187, commercially available from Momentive Performance Materials,Albany, N.Y.

In one embodiment, a wetting agent can be included in the binder coatingcomposition. A wetting agent can improve the contact and wetting betweenthe binder coating composition, the particles mixed with the bindercoating composition, and the current collector substrate. Accordingly,inclusion of a wetting agent can improve the adherence between thevarious components following cure of the binder.

Wetting agents can include both sacrificial materials, which willgenerally be volatized prior to or during the cure of the binder coatingcomposition, as well as materials that can remain in the productfollowing cure. For instance, a wetting agent can also function as anelectrolyte following cure of the binder. Exemplary wetting agents caninclude, without limitation, acetone, isopropyl alcohol, dimethylcarbonate, and the like. In general, any solvent or electrolyte materialthat can improve wetting and contact between the binder coatingcomposition, the particles, and the current collector can be utilized.In one embodiment, fast evaporating, low boiling temperature wettingagents can be preferred. By way of example, a wetting agent can have aboiling point of less than about 160° F. (about 71° C.). Beneficially,by utilization of a low boiling point wetting agent, the wetting agentcan be dissipated during the UV/EB cure, and the substantial thermalenergy input necessary for solvent removal of previously known processesis not necessary. Alternatively, wetting agents can be utilized that aredesigned to remain in the material following the cure, for instance foruse as an electrolyte.

Referring now to the figures, FIGS. 1, 2, and 3 illustrate embodimentsfor applying an electrode particulate material 10 (FIG. 3) and apolymeric binder coating composition 9 (FIG. 3) as an electrode layer 5to an electrode current collector 2. Though shown as separate layers inFIG. 3, the electrode particulate material 10 and the binder coatingcomposition are generally applied to a current collector 2 mixed as asingle electrode layer 5. The polymer of the electrode layer 5 is thencured on the current collector 2 utilizing actinic and/or EB radiation.Following crosslinking to form a matrix adhered to a current collector,the binders can exhibit excellent chemical resistance and can beinsoluble in electrolytes at elevated temperatures while demonstratingexceptional adhesion to current collectors.

Particulate materials 10 as may be incorporated in electrodes caninclude any particulate materials as are generally known in the art suchas, without limitation, carbon particulate materials such as graphene,activated carbon, graphite, low sulfur graphite, carbon nanotubes,silicon-based materials, etc.; metal oxide salts such as oxides oflithium, cobalt, manganese, nickel, or vanadium; and so forth. By way ofexample, particulate materials can include lithium compounds such aslithium manganese oxide, lithium cobalt oxide, lithium nickel oxide,lithium nickel cobalt aluminum oxide, lithium iron phosphate, lithiumnickel manganese cobalt (NMC), and mixtures thereof.

In further detail, referring to FIGS. 1, 2, and 3, an electrode currentcollector feed roll 1 supplies electrode current collector 2. Anapplicator 3 mixes the electrode particulate material 10 with thepolymeric binder coating composition 9 and applies a thin layer 5 of themixed components to moving current collector 2. Of course, the electrodeparticulate material 10 and various components of a binder coatingcomposition 9 may be premixed prior to addition to the applicator 3 ifdesired. For instance, a carbon particulate material and a solid binderpolymer can first be milled, e.g., in a 3 roll mill. Following themixing of the carbon and the binder polymer, lithium compounds and asuitable diluent (as well as any additional components such asadditional crosslinkers or photoinitiators) can be added to the solid,milled mixture, decreasing the melt viscosity of the mixture and formingthe mixture to a spreadable paste of a suitable viscosity.

Applicator 3 applies the mixture as electrode layer 5 to the currentcollector 2. This application coating may be accomplished byconventional coating techniques such as, gravure, flexo, slot die,reverse roll, knife over roll, offset, or the like.

Following formation of the electrode layer 5, the layer can be subjectedto actinic and/or EB radiation, which can crosslink the functionalizedrubber polymers of the electrode layer. For instance, upon subjection ofthe binder coating composition to UV, visible and/or EB radiation and,when necessary, in the presence of a photoinitiator, the crosslinkingagents of the composition can react with the reactive functional groupsof the rubber polymers, forming covalent bonds throughout the layer andthereby firmly encapsulating the particulate material within thecrosslinked network and also firmly binding the electrode material layer5 to the current collector 2.

The resulting application of the electrode layer 5 to electrode currentcollector 2 and the crosslinking thereof with a relatively shortresidence time for actinic radiation curing 4 and/or EB curing 8 canincrease production speeds and reduce costs. Multiple applicatorstations 3 may be employed to build up several layers of electrodecoating materials, optionally with separator layers therebetween, sothat the resulting final thickness required can be accomplished at highspeeds of for example from about 20 FPM to about 400 FPM.

Separators that can be included between layers of electrodes can be anyseparator as is generally known in the art. For instance, when formingan EDLC or a lithium ion battery, a separator can be applied betweenadjacent electrode layers that is formed of a polymeric sheet, such aspolytetrafluoroethylene (PTFE), polypropylene (PP), polyethylene (PE),or fused layers of PP & PE, and the like.

The binder coating composition 9 can generally be present in electrodelayer 5 from about 1 wt. % to about 20 wt. %, for instance from about 2wt. % to about 12 wt. %, from about 2 wt. % to about 6 wt. %, or fromabout 3 wt. % to about 5 wt. %. The coating mixture is generally appliedin a very thin layer 5 to electrode current collector 2. Electrode layer5 thickness may be from about 1 to about 500 microns, from about 5 toabout 250 microns, from about 5 to about 200 microns, or from about 5 toabout 150 microns. An electrode layer 5 may be applied to one or bothsides of the current collector 2. FIGS. 1 and 2 illustrate a systemapplying electrode layer 5 to each side of a current collector 2.

FIGS. 1 and 2 depict systems utilizing both actinic and EB radiationdevices 4 and 8, respectively. Depending on the characteristics of thebinder coating composition, either actinic radiation device 4, EBradiation device 8, or both may be utilized.

Referring to FIG. 1, an electrolyte 6 may be integrated with electrodecurrent collector 2 and electrode layer 5. Electrolyte 6 can be a solid,a liquid, or a gel, as is known in the art. For example, electrolyte 6can be an organic electrolyte, such as a carbonate (e.g., ethylenecarbonate or diethyl carbonate containing complexes of lithium ions), oran aqueous electrolyte, such as potassium hydroxide, sulfuric acid, or aliquid mixture of organic carbonates such as alkyl carbonate containingcomplexes of lithium ions (e.g., non-coordinated anion salts such asLiPF₆, LiAsF₆, LiClO₄, LiBF₄, and LiCF₃SO₃). If electrolyte 6 is liquid,a polymeric separator may be included in electrolyte layer 6. Generally,if electrolyte 6 is a solid or gel, an electrolyte separator is notneeded, though a separator may still be utilized in these embodiments.If an electrode layer 5 is applied to both sides of the currentcollector 2, electrolyte 6 may be integrated on each side of currentcollector 2. The product may then be passed through calendar rolls 7which can compress the layers to a desired thickness. If required,electron beam radiation device 8 may radiate through the electrolyte 6to cure the binding material.

Referring to FIG. 2, illustrated is a process for manufacturing anelectrode that does not incorporate electrolyte 6. The techniquedepicted in FIG. 2 could be combined with the technique depicted in FIG.1 to assemble an electrochemical cell 11 such as shown in FIG. 3. Forexample, the process depicted in FIG. 1 may be utilized to construct theanode or cathode (current collector 2 and electrode layer 5) andelectrolyte 6. The process depicted in FIG. 2 may be utilized toconstruct the opposing electrode without electrolyte 6. The products ofFIGS. 1 and 2 may then be combined to construct an electrochemical cell.

For instance, FIG. 3 generally illustrates a lithium ion electrochemicalcell 11 that may be formed in accordance with the disclosure. Asillustrated, the cell 11 includes current collector 2 with an electrodelayer 5 disposed on each side. The electrode layer 5 includes anode (−)or cathode (+) active material 10 and actinic and/or EB curablepolymeric binder coating 9. FIG. 3 illustrates the electrode material 10and the binder coating 9 as separate layers for convenience ofillustration. Electrolyte 6 and optionally an electrolyte separator (notshown) may be disposed on each electrode layer 5. As one skilled in theart appreciates, a lithium ion battery may comprise any number ofelectrochemical cells 11 in series or parallel as desired. In additionto cell 11, a lithium ion battery constructed in accordance with thedisclosure may further include insulation material, casings, controlcircuitry, connectors, etc. as will be appreciated by those skilled inthe art. Furthermore, the battery can be any type of lithium ion batterysuch as cylindrical, prismatic, pouch-type, or other batteries as areunderstood in the art.

Similarly, a first electrode and a second identical electrode can beassembled with a suitable electrolyte and separator therebetween toconstruct an EDLC. For instance, and with reference to FIG. 4, an EDLC40 can include a first aluminum current collector 42 and a secondaluminum current collector 43. The first and second current collectors42, 43 can be separated by a separator 46. A first layer 44 and a secondlayer 45 on either side of the separator 46 can be the same ordifferent. For instance, both layer 44 and 45 can include an actinic/EBradiation cured binder 50 and particulates 52, e.g. graphite, in amixture. The separator 46 can be any standard separator, for instance aporous PTFE film.

The present disclosure can provide numerous advantages. For instance,disclosed methods may significantly reduce manufacturing costs forelectrodes, and thereby products produced therefrom. The advantages ofthe present disclosure can include, without limitation:

-   -   a) Substantial reduction of processing time for curing electrode        binding materials.    -   b) Significant reduction in capital and operating costs by        eliminating the need for thermal curing ovens and the associated        energy inefficiencies of thermal drying in lieu of actinic        and/or EB radiation curing stations.    -   c) Substantial reduction in space, building, and infrastructure        and maintenance that accompany thermal curing. For example,        existing thermal lines are 100 ft long and run 10-20 ft per        minute; two UV lamps can fit in a length of 2 feet (replacing        100 ft of production line) and produce batteries at 200 ft/min.        So to expand the thermal line to run at the 200 ft/min, the        thermal section of the production line would have to be        increased to 1,000-2,000 ft long or building needs to be an        additional 0.2-0.4 miles long.    -   d) Substantial reduction or elimination of the requirement of        organic solvents which may substantially reduce or eliminate the        costs of Volatile Organic Compound (VOC) procurement, recovery,        and disposal.

The present invention may be better understood with reference to thefollowing examples.

EXAMPLES 1-4

The ability to form a coating on an aluminum substrate that is actinicand/or EB radiation cured and remains adhered to the substrate underlithium ion battery simulated conditions was demonstrated. Four sampleswere tested. The compositions of each sample are shown in Table 1,below. The composition values are reported in percent by weight. Foreach sample, a binder coating composition was coated onto a 2″×2″ sampleof aluminum foil. Each sample was then UV cured and weighed. Followingcuring the sample was placed in a container and immersed in a mixture of40 wt. % ethylene carbonate and 60 wt. % dimethyl carbonate and placedin an oven. The oven was held at approximately 140° F. for two weeks.For approximately one hour of the test time, the oven temperaturereached approximately 180° F. The temperature and atmosphere of the ovenserved to simulate the temperature and electrolyte composition generallyfound in operational lithium ion batteries. The results of the tests arealso shown in Table 1 below.

TABLE 1 Sample 1 2 3 4 CN 120B80Z¹ — — 95.00 — Darocure 4265² 5.00 5.00UC-102³ 47.75 47.03 SR-259⁴ 47.75 95.00 SR-506⁵ 47.03 Esacure KIP 100F⁶4.00 4.00 Irgacure 819⁷ 0.50 0.50 Silquest A-187⁸ 1.43 Total 100.00100.00 100.00 100.00 Weight of aluminum foil (g) 1.2636 1.2685 1.27061.2735 Weight of aluminum foil + 2.7213 2.7216 3.2764 4.4021 UV curedcoating (g) Weight of aluminum foil + 2.7245 2.7254 3.7107 4.7127 UVcured coating after 2 week oven exposure in ethylene carbonate (40 wt.%) + dimethyl carbonate (60 wt. %) atmosphere (g) Adhesion to aluminumafter adhered adhered lifting lifting exposure Structure solid solidswell & lift swell & cracks Percent weight gain after 2 0.2 0.3 21.7 9.9week soak ¹Reactive epoxy acrylate oligomer/monomer mixture availablefrom Sartomer Co., Exton, PA ²UV photoinitiator available from CibaSpecialty Chemicals, Tarrytown, NY ³Reactive liquid rubber oligomeravailable from Kuraray Co. Ltd., Pasadena, TX ⁴Polyethylene glycol 200diacrylate reactive diluent monomer available from Sartomer Co., Exton,PA ⁵Isobornyl acrylate reactive diluent monomer available from SartomerCo., Exton, PA ⁶UV photoinitiator available from Lamberti USA, Inc.,Conshohocken, PA ⁷UV photoinitiator available from Ciba SpecialtyChemicals, Tarrytown, NY ⁸γ-glycidoxypropyltrimethoxysilane couplingagent available from Momentive Performance Materials, Albany, NY

As can be seen, samples 1 and 2 containing UC-102 produced a coatingthat solidly adhered to the aluminum substrate with minimal weight gainafter two weeks immersed in a carbonate mixture. Conversely, sample 3utilizing a reactive epoxy acrylate oligomer/monomer mixture (bisphenolepoxy acrylate oligomer diluted with 20 wt. % hexanediol diacrylate),yielded a coating that delaminated from the aluminum substrate whileincreasing in weight by 21.7%. Likewise, sample 4 composed of 95 wt. %of reactive diluent monomer and 5 wt. % photoinitiator yielded a coatingthat also substantially delaminated while increasing in weight by 9.9%.Sample 1 and 2 are suitable mixtures for electrode binders. Samples 3and 4 demonstrate that more common acrylate mixtures are unsuitable foruse as electrode binders

EXAMPLE 5

An approximately 200 gram mixture of 90 wt. % LiMn₂O₄, 6 wt. % carbonblack and 4 wt. % of a mixture of approximately 50 wt. % UC-102 and 50wt. % isobornyl acrylate reactive diluent was mixed in a laboratoryscale Magnetically Assisted Impact Coating device (MAIC) on a batchbasis. The test resulted in the MAIC device successfully dispersing theliquid mixture of UC-102 and isobornyl acrylate as a coating on thesurface of the solid LiMn₂O₄ and carbon particles.

EXAMPLE 6

The LiMn₂O₄ and carbon particles coated with the mixture of UC-102 andisobornyl acrylate in Example 5 were dried and applied to an aluminumfoil substrate. The material was then EB cured with 50 Mrad exposure.Following EB curing, the aluminum substrate was rotated to observe theadhesion quality of the material to the aluminum. No substantial amountof the material remained adhered to the substrate.

EXAMPLE 7

The LiMn₂O₄ and carbon particles coated with the mixture of UC-102 andisobornyl acrylate in Example 5 were mixed with approximately 40 wt. %by volume of acetone and applied as an approximately 10 mil layer on analuminum foil substrate. The addition of approximately 40% by volumeacetone as a wetting agent reduced the viscosity of the mixturesufficiently for the material to be coated on an aluminum foilsubstrate. The material was then permitted to air dry for a few secondsto allow the acetone to evaporate. After the acetone had sufficientlyevaporated, the material was then EB cured with 50 Mrad exposure.Following EB curing, the aluminum substrate was rotated to observe theadhesion quality of the material to the aluminum. The material remainedsufficiently adhered to the substrate.

EXAMPLE 8

The LiMn₂O₄ and carbon particles coated with the mixture of UC-102 andisobornyl acrylate in Example 5 were mixed with approximately 40% byvolume of dimethyl carbonate electrolyte and applied as an approximately10 mil layer on an aluminum foil substrate. The approximately 40% byvolume of the dimethyl carbonate electrolyte as a wetting agent wasadded to the mixture to improve the contact between the binder and thealuminum. The material was then EB cured with 50 Mrad exposure. Thematerial was not completely dry prior to EB curing. Following EB curing,the aluminum substrate was rotated to observe the adhesion quality ofthe material to the aluminum. The material remained sufficiently adheredto the substrate. This result demonstrates that a wetting agentelectrolyte can improve contact between the binder and the aluminum foilso that when the binder is cured it has better adhesion to the aluminumfoil. The electrolyte has no adhesion to the aluminum foil and does notbecome part of the polymer.

As shown in Examples 6-8, a small amount of wetting agent may be neededin order to improve contact between the binder, particles, and thealuminum foil substrate during actinic or EB radiation polymerization.Example 8 illustrates that an electrolyte material, such as commonlyutilized in lithium ion batteries, may be used as a wetting agent toimprove wetting between the particles, binder and aluminum foilsubstrate. It is recognized that the hydrophilic nature of someelectrolyte materials will require moisture control in the manufacturingprocess.

EXAMPLE 9

A mixture of 90 wt. % LiMn₂O₄ and 4 wt. % carbon particles coated with 6wt. % binder coating composition comprised of 47 wt. % UC-102, 47 wt. %isobornyl acrylate and 4 wt. % Esacure KIP 100F and 0.5 wt. % Irgacure819 photoinitiators and 1.5 wt. % Silquest A-187 coupling agent wasprepared using the Magnetically Assisted Impact Coating technique. Thiscathode coating material was spread to an approximate 26-micronthickness and one inch width using a flat knife to a 26-micron thickaluminum foil substrate that had been cleaned with a 5% acetic acidsolution by submersion for 10 seconds. The coated aluminum foil was thenpassed through a two roller jeweler's press to create greater contactbetween the aluminum foil, solid particles and binder. The structure wasthen exposed with 2 passes under actinic UV radiation utilizing a 400watt/inch D bulb powered by a Miltec MP-400 Power Supply and a FusionI250 irradiator. This procedure was repeated using about 10% to about40% compaction ratios of the cathode coating material in the jewelerspress. Following the UV curing, the aluminum substrate was rotated toobserve the adhesion of the cathode particles to the aluminum and to oneanother. In all cases the particle adhesion to the aluminum wasunsatisfactory, less than 5% adhesion; and the adhesion among particleswas also unsatisfactory, less than 10%.

EXAMPLE 10

A mixture of 90 wt. % LiMn₂O₄ and 4 wt. % carbon particles mixed into 6wt. % binder composition comprised of 47 wt. % UC-102, 47 wt. %isobornyl acrylate and 4 wt. % Esacure® KIP 100F and 0.5 wt. % Irgacure®819 photoinitiators and 1.5 wt. % Silquest® A-187 coupling agent wasprepared using the Magnetically Assisted Impact Coating technique. Thiscathode coating material was mixed by simple stirring in a beaker withapproximately 15 wt. % isopropyl alcohol as a wetting agent. The mixturewas applied to an aluminum foil at an approximately 26-micron thicknessand one inch width using a flat knife substrate. The foil had beencleaned with a 5% acetic acid solution by submersion for 10 seconds. Thecoated foil was then exposed with 2 passes under actinic ultravioletradiation utilizing a 400 watt/inch D bulb powered by a Miltec MP-400Power supply and a Fusion I250 irradiator. The belt speed was adjustedto 20 feet per minute. This procedure was repeated increasing the beltspeed to 50 feet per minute, 100 feet per minute, and then 150 feet perminute. Following the UV curing, the aluminum substrate was rotated toobserve the adhesion quality. Adhesion was good when cured at 20 fpm, 50fpm, and 100 fpm. At 150 fpm, adhesion was good in some areas and poorin other areas, indicating that the cure speed of this formula is lessthan 150 fpm.

EXAMPLE 11

A mixture of 40 wt. % carbon and 60 wt. % binder comprised of 47 wt. %UC-102, 47 wt. % isobornyl acrylate and 4 wt. % Esacure® KIP 100F and0.5 wt. % Irgacure® 819 photoinitiators and 1.5 wt. % Silquest® A-187coupling agent was prepared using a standard 700 RPM stirrer. Thiscarbon and binder mix was then mixed with isopropyl alcohol as a wettingagent and incremental amounts of LiCoO₂ until the final mix was byweight 7.5 wt. % carbon and binder mix, 25 wt. % isopropyl alcohol, and67.5 wt. % LiCoO₂. The mixture was applied to an approximately 26-micronthickness and one inch width using a flat knife to an aluminum foilsubstrate that had been cleaned with a 5% acetic acid solution bysubmersion for 10 seconds. The coated aluminum was exposed to actinicultraviolet radiation utilizing two (2) 400 watt/inch D bulbs powered bya Miltec MP-400 Power supply and a Fusion I250 irradiator. The beltspeed was adjusted to 50 feet per minute. Adhesion of the particles oneto another and of the particles to the aluminum was good. The isopropylalcohol wetting agent was evaporated completely by the brief exposure tothe UV lamp chamber. The curing belt speed was set to 100, 150, and then200 feet per minute. Coating adhesion was tested by folding andinverting the coated aluminum. At all three curing speeds the adhesionwas good. This demonstrated the ability to achieve satisfactory adhesionof carbon and a typical active lithium cathode material to a currentcollector using a UV curable binder mix including a wetting agent toease deposition and the coating cured at up to 200 feet per minuteprocessing speed which equates to a residence time in the UV lampexposure of less than a second.

EXAMPLE 12

A mixture of 40 wt. % carbon and 60 wt. % binder comprised of 47 wt. %CN301, 23.5 wt. % isobornyl acrylate, 23.5 wt. % SR-238 HDODA, and 4.5wt. % SM303 photoinitiator and 1.5 wt. % Genorad 51 dispersing agent wasprepared using a standard 700 RPM stirrer. This carbon and binder mixwas then mixed with isopropyl alcohol as a wetting agent and incrementalamounts of LiCoO₂ until the final mix was by weight 7.5% carbon andbinder mix, 25% isopropyl alcohol, and 67.5% LiCoO₂. The mixture wasapplied to an approximately 26-micron thickness and one inch width usinga flat knife to an aluminum foil substrate that had been cleaned with a5% acetic acid solution by submersion for 10 seconds. The coatedaluminum was exposed to actinic ultraviolet radiation utilizing two (2)400 watt/inch D bulbs powered by a Miltec MP-400 Power supply and aFusion I250 irradiator. The belt speed was adjusted to 50 feet perminute. Adhesion of the particles one to another and of the particles tothe aluminum was good. The belt speed was adjusted to 100, 150, and 200feet per minute and adhesion tested by folding and inverting the coatedaluminum. In all cases, adhesion was good.

EXAMPLE 13

A mixture of 40 wt. % carbon and 60 wt % binder comprised of 47 wt. %CN301, 47 wt. % isobornyl acrylate and 4 wt. % Esacure® KIP 100F and 0.5wt. % Irgacure® 819 photoinitiators and 1.5 wt. % Silquest® A-187coupling agent was prepared using a standard 700 RPM stirrer. Thiscarbon and binder mix was then mixed with isopropyl alcohol as a wettingagent and incremental amounts of LiCoO₂ until the final mix was byweight 7.5% carbon and binder mix, 25% isopropyl alcohol, and 67.5%LiCo₂O₄. The mixture was applied to an approximately 26-micron thicknessand one inch width using a flat knife to an aluminum foil substrate thathad been cleaned with a 5% acetic acid solution by submersion for 10seconds. The coated aluminum was exposed to actinic ultravioletradiation utilizing two (2) 400 watt/inch D bulbs powered by a MiltecMP-400 Power supply and a Fusion I250 irradiator. The belt speed wasadjusted to 200 feet per minute and adhesion tested by folding andinverting the coated aluminum. Adhesion was good. The coated aluminumcoupon was then immersed in a mixture of 60%/40% dimethyl/ethylenecarbonate and held at 140° F. for 2 weeks. At the end of the two weektesting period weight gain was essentially zero and adhesion to thealuminum and to the particles was good. This demonstrates a cathodecoating was applied using UV curable binder blend and cured at aprocessing speed of 200 feet per minute and exposure time to UVradiation of less than one second retained adhesion and physicalintegrity after exposure to a Lithium-ion battery electrolyteenvironment for 2 weeks.

EXAMPLE 14

A mixture of 40 wt. % carbon and 60 wt. % binder comprised of 47 wt. %CN301, 23.5 wt. % isobornyl acrylate, 23.5 wt. % CD563 AHDODA, and 4.5wt. % SM303 photoinitiator and 1.5 wt. % Genorad 51 dispersing agent wasprepared using a standard 700 rpm stirrer. This carbon and binder mixwas then mixed with isopropyl alcohol as a wetting agent and incrementalamounts of LiCoO₂ until the final mix was by weight 7.5% carbon andbinder mix, 25% isopropyl alcohol, and 67.5% LiCoO₂. The mixture wasapplied to an approximate 26-micron thickness and one-inch width using aflat knife to an aluminum foil substrate that had been cleaned with a 5%acetic acid solution by submersion for 10 seconds. The coated aluminumwas exposed to actinic radiation utilizing two (2) 400 watt/inch D bulbspowered by a Miltec MP-400 Power supply and a Fusion I250 irradiator.The belt speed was adjusted to 200 feet per minute and adhesion testedby folding and inverting the coated aluminum. Adhesion was good. Thecoated aluminum coupon was then immersed in a mixture of 60%/40%dimethyl/ethylene carbonate and held at 140° F. for 2 weeks. At the endof the two week testing period weight gain was essentially zero andadhesion to the aluminum and the particles one to another was good.

EXAMPLES 15-17

The ability to utilize UV curable binders in the formulation of alithium-ion battery cathode that can be satisfactorily charged anddischarged through multiple cycles with performance typical of alithium-ion battery cathode using typical active electrode compoundssuch as LiCoO₂ and LiMn₂O₄ was demonstrated. Three samples were tested.The cathode current collector coating compositions are shown in Table 2below. Each sample consisted of an approximate 2 inch by 6 inch piece of26-micron thick aluminum sheet initially coated with a combination ofbinder blend, carbon, lithium compound, and isopropyl alcohol as awetting agent. The binder blend and the carbon were first mixed in aD-10 mixer available from H. Duke Enterprises of Pleasant View, Tenn.Further mixing to ensure a homogeneous blend was accomplished using anEXAKT Model 80S Three Roll Mill available from EXAKT Technologies,Oklahoma City, Okla. The binder mix, carbon, lithium compound, andisopropyl alcohol as a wetting agent were mixed in the proportions shownunder the heading “Coating” in Table 2 below. The same D-10 mixer ofabove was used for mixing the components. The coating mix was applied tothe aluminum sheet current collector using a micrometer adjusted knifeedge applicator set to a thickness of 75 microns. The coated currentcollector samples were cured at various speeds as depicted in Table 2under 2, 600 Watt/inch, 10″ long, D type UV lamps. As a result of the UVcuring process only the carbon, binder blend and lithium compoundsremained on the current collector in the proportions shown under theheading “Cured Coating” in Table 2 below. All three samples emerged fromthe UV curing lamps with very good adhesion of the carbon and lithiumcompound particles to the current collector and to one another. Allthree samples were calendered in a roll press from 75-microns thicknessto 50-micron thickness. The samples were shipped to the US Department ofEnergy Argonne National Laboratory for electrochemical testing.

At the test laboratory, a circular coupon the diameter of a 2032 CoinCell was cut from each sample. The UV cured cathodes were assembled into2032 coin half cells using lithium metal as the anode, Celgard 2325 asthe separator (a PP/PE/PP trilayer film from Celgard, LCC in Charlotte,N.C.), and 1.2 molar LiPF6 in ethylene carbonate:ethylmethylcarbonate(3:7 by weight) as the electrolyte. The half cells were assembled in aHelium inserted glove box and subjected to electrochemicalcharge/discharge testing utilizing a Maccor 4400 electrochemical testapparatus.

TABLE 2 Example 15 Example 16 Example 17 Example 18-19 Binder and CarbonMix Weight % Weight % Weight % Weight % C107¹ 6.00% 6.00% 0.00% 0.00%ITX² 2.00% 2.00% 0.00% 1.00% Irgacure 819³ 0.20% 0.20% 2.00% 0.00%Chivacure 184⁸   0%   0% 5.00% 5.00% Chivacure 169¹³   0%   0% 0.00%4.00% CD564⁹   0%   0% 24.00%  20.00%  SR506⁴ 22.80%  22.80%  24.00% 25.00%  SR238⁵ 23.00%  23.00%  0.00% 5.00% CN301⁶ 20.00%  20.00%  0.00%0.00% CN307¹⁰   0%   0% 20.00%  25.00%  Gen 51⁷ 6.00% 6.00% 0.00% 0.00%NMP¹⁵ 0.00% 0.00% 0.00% 15.00%  Carbon Super P¹⁰ 20.00%  20.00%  25.00% 0.00% Total 100.00%  100.00%  100.00%  100.00%  Coating Binder Mix   16%  16%  2.8% 24.00%  Carbon P   4%   4%  8.4% 0.00% LiMn₂O₄ ¹¹   30%  30% 58.8% 0.00% LiCoO₂ ¹²   30%   30%  0.0% 0.00% Graphite ESLP10¹⁴  0%   0%  0.0% 36.00%  Isopropyl Alcohol   20%   20% 30.0% 40.00%  100%  100% 100.0%  100.0%  Coating thickness 75 microns 75 microns 75microns 75 microns Curing Speed 150 feet per 200 feet per 100 feet per200 feet per minute minute minute minute Calendered Thickness 50 microns50 microns 50 microns 50 microns Cured Coating LiMn₂O₄ 37.5% 37.5%   84%0.00% LiCoO₂ 37.5% 37.5%   0% 0.00% Binder Mix   20%   20%   12% 40.00% Graphite   0%   0%   0% 60.00%  Carbon P   5%   5%   4% 0.00%¹Photoiniator available from Chitec Technology, Corp. Taipei, Taiwan²Photosensitizer available from Chitec Technology Corp. Taipei, Taiwan³UV photoinitiator available from Ciba Specialty Chemicals, Tarrytown,NY ⁴Isobornyl acrylate reactive diluent monomer available from SartomerCo., Exton, PA ⁵Hexanedioldiacrylate reactive diluent monomer availablefrom Sartomer Co., Exton, PA ⁶Polybutadienedimethylacrylate oligomeravailable from Sartomer Co., Exton, PA ⁷Dispersant available from RahnUSA Corp, Aurora, IL ⁸Photoiniator available from Chitec Technology,Corp., Taipei, Taiwan ⁹Alkoxylatedhexanedioldiacrylate reactive diluentmonomer available from Sartomer Co., Exton, PA ¹⁰Carbon powder availablefrom Sigma-Aldrich, Co, St. Louis, MO ¹¹Lithium Cobalt Oxide availablefrom Sigma-Aldrich, Co, St Louis MO ¹²Lithium Manganese Oxide availablefrom Sigma-Aldrich, Co, St Louis, MO ¹³Photoinitiator available fromChitec Technology, Corp,, Taipei, Taiwan ¹⁴Graphite available fromTimcal Graphite and Carbon, Westlake, Ohio ¹⁵N-Methyl-2-Pyrrolidoneavailable from Worldchem, LTD, Hafei, Anhui, China

The electrochemical test results of the initial charge and discharge ofexamples 15, 16, and 17 are shown in FIGS. 5, 6, and 7, respectively.Sample 1 corresponds to Example 15 (FIG. 5); Sample 2 corresponds toExample 16 (FIG. 6); and Sample 3 corresponds to Example 17 (FIG. 7).Sample 1 (Example 15) was subsequently subjected to cyclic charge anddischarge. Sample 1 was charged and discharged at the C/5 rate of 24milliamperes/gram and it retained 61% of the initial charge capacityafter ten cycles.

The composition of Example 15 included LiCoO₂/LiMn₂O₄ of approximately7.4 mg/cm² of active material. The current density was C/5, 24 mA/g, andthe cut-off voltage was 3.0-4.3 V. The charge capacity was 130 mAh/g andthe discharge capacity was 105 mAh/g.

The composition of Example 16 included LiCoO₂/LiMn₂O₄ of approximately5.2 mg/cm² of active material. The current density was C/5, 24 mA/g, andthe cut-off voltage was 3.0-4.3 V. The charge capacity was 101 mAh/g andthe discharge capacity was 61 mAh/g.

The composition of Example 17 included LiMn₂O₄ of approximately 5.2mg/cm² of active material. The current density was C/5, 24 mA/g, and thecut-off voltage was 3.0-4.3 V. The charge capacity was 107 mAh/g and thedischarge capacity was 54 mAh/g.

EXAMPLE 18

The ability to utilize UV curable binders in the formulation of alithium-ion battery anode coating on a current collector that can retainintegrity and adhesion in the presence of a typical Lithium ion batteryelectrolyte was demonstrated. A UV curable binder mix was prepared usingconventional mixing techniques in the proportions shown in Table 2,Examples 18-19 under the heading, “Binder and Carbon Mix”. Graphite wasadded to the UV curable binder mix to comprise an anode coating mixtureusing conventional mixing techniques in the proportions shown in Table2, Examples 18-19 under the heading, “Coating”. The coating mix wasapplied to a 26 micron thick copper foil current collector using amicrometer adjusted knife edge applicator set to a thickness of 75microns and exposed to actinic radiation utilizing two (2) 400 watt/inchD bulbs powered by a Miltec MP-400 Power supply and a Fusion I250irradiator at a speed of 200 feet per minute. During exposure to the UVradiation, the isopropyl alcohol evaporated. The cured coating wascalendered to 50 micron thickness. Following curing and calendering, atwo inch by two inch coupon of the coated current collector was thenimmersed in a mixture of 60%/40% dimethyl/ethylene carbonate and held at140° F. for one week. At the end of the one week testing period weightgain was essentially zero and adhesion to the copper and the particlesone to another was good.

EXAMPLE 19

The ability to utilize UV curable binders in the formulation of anElectric Double Layer Capacitor (EDLC) electrode coating on a currentcollector that can retain integrity and adhesion in the presence of atypical EDLC electrolyte was demonstrated. A UV curable binder mix wasprepared using conventional mixing techniques in the proportions shownin Table 2, Examples 18-19 under the heading, “Binder and Carbon Mix”.Graphite was added to the UV curable binder mix to comprise an electrodecoating mixture using conventional mixing techniques in the proportionsshown in Table 2, Examples 18-19 under the heading, “Coating”. Thecoating mix was applied to a 26 micron thick aluminum foil currentcollector using a micrometer adjusted knife edge applicator set to athickness of 75 microns and exposed to actinic radiation utilizing two(2) 400 watt/inch D bulbs powered by a Miltec MP-400 Power supply and aFusion I250 irradiator at a speed of 200 feet per minute. Duringexposure to the UV radiation, the isopropyl alcohol evaporated. Thecured coating was calendered to 50 micron thickness. Following curingand calendering, a two inch by two inch coupon of the coated currentcollector was then immersed in a mixture of 60%/40% dimethyl/ethylenecarbonate and held at 140° F. for one week. At the end of the one weektesting period weight gain was essentially zero and adhesion to thealuminum and the particles one to another was good.

While the foregoing written description enables one of ordinary skill tomake and use what is considered presently to be the best mode thereof,those of ordinary skill will understand and appreciate the existence ofvariations, combinations, and equivalents of the specific embodiment,method, and examples herein. The disclosure should therefore not belimited by the above described embodiments, methods, and examples, butby all embodiments and methods within the scope and spirit of thedisclosure as claimed.

What is claimed is:
 1. An electrode comprising a current collector and apolymeric layer adhered to a surface of the current collector, thepolymeric layer comprising a crosslinked matrix, the crosslinked matrixincluding a crosslink reaction product of a rubber oligomer precursorreacted with an electron beam or actinic radiation curable crosslinkingagent, the rubber oligomer precursor comprising a backbone and areactive functionality pendent to the backbone, the reactivefunctionality of the precursor comprising carboxy functionality,acrylate functionality, vinyl functionality, vinyl ether functionality,meth(acrylate) functionality, or epoxy functionality, the functionalityof the precursor being reacted with the crosslinking agent such that thecrosslinked matrix includes the crosslinking agent covalently bonded tothe rubber oligomer, the crosslinked matrix being electron beam oractinic radiation cured, the polymeric layer further comprisingparticulate material, wherein the polymeric layer is conductive, whereinthe electrode is adjacent to an additional layer, and the additionallayer comprises an electrolyte.
 2. The electrode according to claim 1,wherein the rubber oligomer that is covalently bonded to crosslinkingagent includes at least one of isoprene monomer units, butadiene monomerunits, cyclopentadiene monomer units, ethylidene norbornene monomerunits, vinyl norbornene monomer units, or combinations thereof.
 3. Theelectrode according to claim 1, wherein the rubber oligomer precursor isa (meth)acrylated rubber oligomer having a carboxylated isoprenebackbone of the formula:

wherein m is between about 100 and about 1500, and n is between 1 andabout
 20. 4. The electrode according to claim 1, wherein the rubberoligomer precursor is a (meth)acrylated rubber oligomer having acarboxylated butadiene backbone of the formula:

wherein m is between about 10 and about 1000, and n is between 1 andabout
 20. 5. The electrode according to claim 1, wherein the rubberoligomer precursor is a (meth)acrylated rubber oligomer having abutadiene backbone of the formula:

wherein n is between about 5 and about
 2000. 6. The electrode accordingto claim 1, wherein the particulate material comprises carbon.
 7. Theelectrode according to claim 6, wherein the carbon is graphene,activated carbon, graphite, low sulfur graphite, carbon nanotubes, orcombinations thereof.
 8. The electrode according to claim 1, wherein theparticulate material comprises a metal oxide salt.
 9. The electrodeaccording to claim 1, wherein the polymeric layer defines a thicknessbetween about 1 and about 500 microns.
 10. A battery comprising theelectrode of claim
 1. 11. The battery according to claim 10, wherein thebattery is a lithium ion battery.
 12. An electric double layer capacitorcomprising the electrode of claim
 1. 13. The electrode according toclaim 1, wherein the crosslinking agent is a reactive diluent.
 14. Theelectrode according to claim 1, wherein the polymeric layer furthercomprises a photoinitiator.
 15. An electrode comprising a currentcollector and a polymeric layer adhered to a surface of the currentcollector, the polymeric layer comprising a crosslinked matrix, thecrosslinked matrix including a crosslink reaction product of a rubberoligomer precursor reacted with an electron beam or actinic radiationcurable crosslinking agent, the rubber oligomer precursor comprising abackbone and a reactive functionality pendent to the backbone, therubber oligomer precursor having a melt viscosity at 38° C. of less thanabout 2000 Pascal seconds, the reactive functionality of the precursorcomprising carboxy functionality, acrylate functionality, vinylfunctionality, vinyl ether functionality, meth(acrylate) functionality,or epoxy functionality, the functionality of the precursor being reactedwith the crosslinking agent such that the crosslinked matrix includesthe crosslinking agent covalently bonded to the rubber oligomer, thecrosslinked matrix being electron beam or actinic radiation cured, thepolymeric layer further comprising particulate material that isencapsulated within the crosslinked matrix, wherein the polymeric layeris conductive, wherein the electrode is adjacent to an additional layer,and the additional layer comprises an electrolyte.
 16. The electrodeaccording to claim 15, wherein the rubber oligomer that is covalentlybonded to crosslinking agent includes at least one of isoprene monomerunits, butadiene monomer units, cyclopentadiene monomer units,ethylidene norbornene monomer units, vinyl norbornene monomer units, orcombinations thereof.
 17. The electrode according to claim 15, whereinthe rubber oligomer precursor is a (meth)acrylated rubber oligomerhaving a butadiene backbone of the formula:

wherein n is between about 5 and about
 2000. 18. The electrode accordingto claim 15, wherein the polymeric layer defines a thickness betweenabout 1 and about 500 microns.
 19. The electrode according to claim 15,wherein the crosslinking agent is a reactive diluent.
 20. The electrodeaccording to claim 15, wherein the polymeric layer further comprises aphotoinitiator.
 21. A battery comprising the electrode of claim
 15. 22.The battery according to claim 21, wherein the battery is a lithium ionbattery.
 23. An electrode comprising a current collector and a polymericlayer adhered to a surface of the current collector, the polymeric layercomprising a crosslinked matrix, the crosslinked matrix including acrosslink reaction product of a rubber oligomer precursor reacted withan electron beam or actinic radiation curable crosslinking agent, therubber oligomer precursor comprising a backbone and a reactivefunctionality pendent the backbone, the reactive functionality of theprecursor comprising carboxy functionality, acrylate functionality,vinyl functionality, vinyl ether functionality, meth(acrylate)functionality, or epoxy functionality, the functionality of theprecursor being reacted with the crosslinking agent such that thecrosslinked matrix includes the crosslinking agent covalently bonded tothe rubber oligomer, the crosslinked matrix being electron beam oractinic radiation cured, the polymeric layer further comprisingparticulate material, wherein the polymeric layer is conductive, whereinthe particular material comprises a lithium compound.
 24. The electrodeaccording to claim 23, wherein the rubber oligomer that is covalentlybonded to crosslinking agent includes at least one of isoprene monomerunits, butadiene monomer units, cyclopentadiene monomer units,ethylidene norbornene monomer units, vinyl norbornene monomer units, orcombinations thereof.
 25. The electrode according to claim 23, whereinthe rubber oligomer precursor is a (meth)acrylated rubber oligomerhaving a butadiene backbone of the formula:

wherein n is between about 5 and about
 2000. 26. The electrode accordingto claim 23, wherein the electrode is adjacent to an additional layer.27. The electrode according to claim 26, wherein the additional layer isa second electrode or a separator.
 28. The electrode according to claim26, wherein the additional layer comprises an electrolyte.
 29. Theelectrode according to claim 23, wherein the polymeric layer defines athickness between about 1 and about 500 microns.
 30. A batterycomprising the electrode of claim
 23. 31. The battery according to claim30, wherein the battery is a lithium ion battery.
 32. An electrodecomprising a current collector and a polymeric layer adhered to asurface of the current collector, the polymeric layer comprising acrosslinked matrix, the crosslinked matrix including a crosslinkreaction product of a rubber oligomer precursor reacted with an electronbeam or actinic radiation curable crosslinking agent, the rubberoligomer precursor comprising a backbone and a reactive functionalitypendent the backbone, the rubber oligomer precursor having a meltviscosity at 38° C. of less than about 2000 Pascal seconds, the reactivefunctionality of the precursor comprising carboxy functionality,acrylate functionality, vinyl functionality, vinyl ether functionality,meth(acrylate) functionality, or epoxy functionality, the functionalityof the precursor being reacted with the crosslinking agent such that thecrosslinked matrix includes the crosslinking agent covalently bonded tothe rubber oligomer, the crosslinked matrix being electron beam oractinic radiation cured, the polymeric layer further comprisingparticulate material that is encapsulated within the crosslinked matrix,the particulate material comprising a lithium compound, wherein thepolymeric layer is conductive.
 33. The electrode according to claim 32,wherein the rubber oligomer that is covalently bonded to crosslinkingagent includes at least one of isoprene monomer units, butadiene monomerunits, cyclopentadiene monomer units, ethylidene norbornene monomerunits, vinyl norbornene monomer units, or combinations thereof.
 34. Theelectrode according to claim 32, wherein the rubber oligomer precursoris a (meth)acrylated rubber oligomer having a butadiene backbone of theformula:

wherein n is between about 5 and about
 2000. 35. The electrode accordingto claim 32, wherein the electrode is adjacent to an additional layer.36. The electrode according to claim 35, wherein the additional layer isa second electrode or a separator.
 37. The electrode according to claim35, wherein the additional layer comprises an electrolyte.
 38. Theelectrode according to claim 32, wherein the polymeric layer defines athickness between about 1 and about 500 microns.
 39. The electrodeaccording to claim 32, wherein the crosslinking agent is a reactivediluent.
 40. The electrode according to claim 32, wherein the polymericlayer further comprises a photoinitiator.
 41. A battery comprising theelectrode of claim
 32. 42. The battery according to claim 32, whereinthe battery is a lithium ion battery.
 43. A battery comprising anelectrode, the electrode of the battery comprising a current collectorand a polymeric layer adhered to a surface of the current collector, thepolymeric layer comprising a crosslinked matrix, the crosslinked matrixincluding a crosslink reaction product of a rubber oligomer precursorreacted with an electron beam or actinic radiation curable crosslinkingagent, the rubber oligomer precursor comprising a backbone and areactive functionality pendent the backbone, the reactive functionalityof the precursor comprising carboxy functionality, acrylatefunctionality, vinyl functionality, vinyl ether functionality,meth(acrylate) functionality, or epoxy functionality, the functionalityof the precursor being reacted with the crosslinking agent such that thecrosslinked matrix includes the crosslinking agent covalently bonded tothe rubber oligomer, the crosslinked matrix being electron beam oractinic radiation cured, the polymeric layer further comprisingparticulate material, wherein the polymeric layer is conductive.
 44. Thebattery according to claim 43, wherein the rubber oligomer that iscovalently bonded to crosslinking agent includes at least one ofisoprene monomer units, butadiene monomer units, cyclopentadiene monomerunits, ethylidene norbornene monomer units, vinyl norbornene monomerunits, or combinations thereof.
 45. The battery according to claim 43,wherein the rubber oligomer precursor is a (meth)acrylated rubberoligomer having a butadiene backbone of the formula:

wherein n is between about 5 and about
 2000. 46. The battery accordingto claim 43, wherein the electrode is adjacent to an additional layer.47. The battery according to claim 46, wherein the additional layer is asecond electrode or a separator.
 48. The battery according to claim 43,wherein the polymeric layer defines a thickness between about 1 andabout 500 microns.
 49. The battery according to claim 43, wherein thebattery is a lithium ion battery.
 50. A battery comprising an electrode,the electrode of the battery comprising a current collector and apolymeric layer adhered to a surface of the current collector, thepolymeric layer comprising a crosslinked matrix, the crosslinked matrixincluding a crosslink reaction product of a rubber oligomer precursorreacted with an electron beam or actinic radiation curable crosslinkingagent, the rubber oligomer precursor comprising a backbone and areactive functionality pendent the backbone, the rubber oligomerprecursor having a melt viscosity at 38° C. of less than about 2000Pascal seconds, the reactive functionality of the precursor comprisingcarboxy functionality, acrylate functionality, vinyl functionality,vinyl ether functionality, meth(acrylate) functionality, or epoxyfunctionality, the functionality of the precursor being reacted with thecrosslinking agent such that the crosslinked matrix includes thecrosslinking agent covalently bonded to the rubber oligomer, thecrosslinked matrix being electron beam or actinic radiation cured, thepolymeric layer further comprising particulate material that isencapsulated within the crosslinked matrix, wherein the polymeric layeris conductive.
 51. The battery according to claim 50, wherein the rubberoligomer that is covalently bonded to crosslinking agent includes atleast one of isoprene monomer units, butadiene monomer units,cyclopentadiene monomer units, ethylidene norbornene monomer units,vinyl norbornene monomer units, or combinations thereof.
 52. The batteryaccording to claim 50, wherein the rubber oligomer precursor is a(meth)acrylated rubber oligomer having a butadiene backbone of theformula:

wherein n is between about 5 and about
 2000. 53. The battery accordingto claim 50, wherein the electrode is adjacent to an additional layer.54. The battery according to claim 53, wherein the additional layer is asecond electrode or a separator.
 55. The battery according to claim 50,wherein the polymeric layer defines a thickness between about 1 andabout 500 microns.
 56. The battery according to claim 50, wherein thecrosslinking agent is a reactive diluent.
 57. The battery according toclaim 50, wherein the polymeric layer further comprises aphotoinitiator.
 58. The battery according to claim 50, wherein thebattery is a lithium ion battery.